Built detergent compositions



B. H. GEDGE Ill BUILT DETERGENT COMPOSITIONS Filed Sept. 23, 1964 July9, 1968 MAYA Amvmn v \{g NTA INVENTOR.

Burion H. Gedge lIL Wcwdu ATTORNEY United States Patent 3,392,121 BUILTDETERGENT COMPOSITIONS Burton H. Gedge 1H, Wyoming, Ohio, assignor toThe Procter & Gamble Company, Cincinnati, Ohio, a corporation of OhioContinuation-impart of application Ser. No. 235,327,

Nov. 5, 1962. This application Sept. 23, 1964, Ser.

11 Claims. (Cl. 252--136) This invention relates to built detergentcompositions of solid and liquid form for heavy duty laundering use, andis based on the discovery of unexpected and remarkable synergisticbuilding actions in mixtures or blends of water soluble inorganicbuilder salts and one or both of two organic builder materials. Thisapplication is a continuation-in-part of copending application Ser. No.235,-- 327, filed Nov. 5, 1962, and now abandoned.

It has been known that when certain substances are added in relativelylarge amounts to the active synthetic detergent component or componentsof washing compositions, an increase in cleaning ability or whitenessmaintenance or both is obtained, even though the washing solution usedmay contain less of the active detergent. Substances capable ofproducing this effect are known as builders. Cleaning ability is theability of a solution of the detergent composition to remove soil fromcloth. Whiteness maintenance relates to the ability of a detergentsolution to prevent suspended soil from depositing on the cloth duringthe washing operation. The term detergency as used herein is intended toembrace both cleaning ability and whiteness maintenance.

Building effects have been noted in connection with various inorganicsalts, such as alkali metal carbonates, bicarbonates, borates,phosphates and silicates. The best of the inorganic builders are thewater soluble polyphosphates, and in particular the water solublepyrophosphates and tripolyphosphates. Of these, sodium tripolyphosphateis the builder most generally used in solid detergent compositions. Inthe formulation of liquid detergent compositions, water solublepyrophosphates are generally preferred because of the tendency oftripolyphosphates to hydrolyze in aqueous solution during long periodsof storage, forming some pyrophosphate and some orthophosphate, thelatter being a less efficient builder and having among otherdisadvantages a detrimental effect on the softness of the fabrics beingtreated. In liquid formulations, also, the potassium salts of inorganicbuilders are sometimes used to take advantage of their greatersolubility.

Useful building actions with the water soluble polyphosphates are notedin detergent compositions in which the ratio of active syntheticdetergent to polyphosphate extends generally from about 1:1 to 1:10.Currently, the most widely sold built detergent compositions containfrom about 1 part to about 7 parts of polyphosphate for each part ofactive synthetic detergent.

Building actions have also hitherto been noted in connection withcertain organic salts.

The nature of the building action is not fully understood. There appearsto be a connection between the ability of a builder to soften the waterwhich is used to make up the washing solution, and the improved resultsin detergency obtained when the builder is used. But not all materialswhichact to sequester hardness-imparting calcium and magnesium ionsperform satisfactorily as builders. Further, useful building actionswith the most effective builders can be noted both above and below thepoint at which the builder is present in the washing solution instoichiometric proportions to the hardness in water.

1 Detergency itself is a complex phenomenon believed to involve verymany factors. Among the aspects of built "ice detergency systems, withrespect to which builders are thought to have useful effects, are suchfactors as stabilization of suspended solid soils, emulsification ofsoils, the surface activity of the aqueous detergent solution, thesolubilization of water-insoluble materials, foaming or suds producingcharacteristics of the washing solutions, peptization of soilagglomerates, neutralization of acid soils, and the like, in addition tothe sequestration of mineral constituents present in the washingsolution. The action, therefore, of different builders varies, and nogeneral basis has been found either in physical properties or inchemical structure upon which one can predict in advance the excellence,ranking or performance of chemical materials or mixtures thereof asdetergency builders.

It should also be kept in mind that the effect of any given detergentcomposition when used in solution to perform a washing operation willvary with such factors as concentration, temperature, the nature of thesoil, the nature of the active detergent ingredient, the amount ofactive ingredient in the solution, the ratio of builder to activeingredient, the hardness of the water and the like. An active ingredienthaving in itself a low detergency value may appear to be helped more bya given quantity of a given builder than would an active detergentingredient having superior detersive properties.

The ratio of builder to active detergent in a detergent composition isconveniently expressed in parts by weight. Where a comparison is to bemade between a builder material which is a mixture of ingredients invarying proportions, this can often best be done by selecting a suitableactive ingredient o-r surfactant, selecting a formulation containing arepresentative ratio of surfactant to a standard building ingredient,and then making up compositions for use by substituting portions ofother builder ingredients for portions of the standard builderingredient on a molar basis. Test results obtained with the variouscompositions so produced will be indicative and will be affected byfewer variables than otherwise.

A basic object of the invention is the attainment of an enhancedbuilding action with a corresponding increase in the above noteddesirable qualities associated with built detergent compositions. Thesynergistic action in the detergent compositions to which this inventionis addressed manifests itself in improvements in one or more or all ofthese qualities, but notably in improved whiteness maintenance.

It is an object of the invention to attain an enhanced building action,particularly in heavy-duty laundry detergent compositions which, so faras is known, is the most effective building action ever attained in suchcompo sitions.

It is an object of the invention to provide a synergistic buildermixture having building properties substantially greater than theadditive contributions of the components thereof.

It is an object of the invention to provide detergent compositions whichare effective in water solutions over a wide range of concentrationsinasmuch as the conditions under which household laundry is done varyquite widely with the individual.

It is an object of the invention to provide detergent compositions inwhich the proportion of active ingredient can be increased, if desired,without sacrificing building action.

It is an object of the invention to provide detergent compositions whichare effective for heavy duty laundering over a Wide range of temperatureand in particular at temperatures in the lower part of the range.

According to this invention, these objects are obtained and anunexpected and surprising synergistic building action is displayed bymixtures of a water soluble salt of ethane-l-hydroxy-l, l-diphosphonicacid and a builder selected from the group consisting of water solubleinorganic polyphosphate builders, particularly the soluble salts oftripolyphosphates and pyrophosphates, and water soluble salts ofnitrilotriacetic acid, and, preferably mixtures thereof in theproportion-s hereinafter described.

Reference is made to the accompanying drawing which is a ternary diagramillustrating the proportions (on a molar basis) in which the buildermixtures of this invention exhibit a surprising and unexpectedsynergistic building action as hereinafter described.

The essential organic builder salts of this invention are derivatives ofethane-l-hydroxy-l, I-diphosphonic acid which has the molecular formulaCH C(OH) (PO H According to nomenclature by radicals, the acid mightalso be named l-hydroxyeth-ylidene diphosphonic acid.

The most readily crystallizable form of the builder compound is obtainedwhen three of the acid hydrogens are replaced by sodium. Hence, the saltcommonly prepared is the trisodium salt which gives a pH near 9.5 indistilled water. The anhydrous trisodium salt has the structureCHs-(f-OH 3Na+ P Can It crystallizes normally as the hexahydrate, whichloses some water during air-drying to yield a mixture of hexaandmono-hydrate averaging 3 to 4 molecules of water of hydration. It ismore stable toward hydrolysis than ordinary condensed polyphosphates,and is compatible with them.

While any alkali metal or ammonium or substituted ammonium salt form canbe used in the practice of this invention, the tetrasodium salt, thetrisodium salt and mixtures thereof are the preferred forms. Mixtures ofthe tetrasodium and trisodium salts give a pH in water solution fromabout 9.5 to 11.5. Each of the lesser neutralized forms such asmonosodium and disodium derivatives or the free acid have comparablebuilder capacities to the trisodium and tetrasodium salt forms providedthat additional alkali is added to adjust the pH of the washing solutionto about 9 to about 12. The standard alkaline materials can be used forthis purpose, such as alkali metal silicates, phosphates, borates andcarbonates. Free alkali materials such as sodium and potassiumhydroxides can also be used. For brevity herein, the soluble salts ofethane-l-hydroxy-l, l-diphosphonic acid will be referred to as EHDP.

The inorganic builder salts of this invention are primarily the sodiumand potassium salts of tripolyphosphoric and pyrophosphoric acids. Otherinorganic substances may be present in addition, such as those mentionedabove. Other soluble salts of tripolyphosphoric and pyrophosphoric acidsmay be employed such as those utilizing other alkali metals as thecation or a cation chosen from ammonium or substituted ammoniumradicals. Sodium or potassium tripolyphosphates have an advantage oversodium or potassium pyrophosphate, especially in whiteness maintenanceand in the feel of fabrics washed in solutions thereof; but both areeffective builders. For brevity, the inorganic water solublepolyphosphate builder salts are referred to hereinafter as STP,exemplifying sodium tripolyphosphate.

Water-soluble salts of nitrilotriacetic acid have the formula CHzC O OHNCH2O O O H CHzC O O H wherein a suitable cation is substituted for theacidic hydrogens in the above formula, the cation being sodium,potassium, other alkali metals or ammonium or substituted ammoniumradicals. The trisodium salt of nitrilotriacetic acid is most generallyused. The soluble salts of 4 nitrilotriacetic acid will be referred toherein for brevity as NTA.

It has been found that the builder mixtures of this invention exhibitimportant building properties with a very wide range of active detergentsubstances and mixtures thereof, and are compatible with the adjuvantsnormally used in detergent compositions. The detergent substancesinclude anionic synthetic non-soap detergents, nonionic syntheticdetergents, ampholytic synthetic detergents-and zwitterionic syntheticdetergents and mixtures thereof. These substances are outlined more atlength as follows:

(a) Anionic synthetic non-soap detergents can be broadly described asthe water-soluble salts, particularly the alkali metal salts, of organicsulfuric reaction products having in their molecular structure an alkylradical cont aining from about 8 to about 22 carbon atoms and a radicalselected from the group consisting of sulfonic acid and sulfuric acidester radicals. (Included in the term alkyl is the alkyl portion ofhigher acyl radicals.) Important examples of the synthetic detergentswhich form a part of the preferred compositions of the present inventionare the sodium or potassium alkyl sulfates, especially those obtained bysulfa-ting the higher alcohols (C -C carbon atoms) produced by reducingthe glycerides of tallow or coconut oil; sodium or potassium alkylbenzene sulfonates, in which the alkyl group contains from about 9 toabout 15 carbon atoms, especially those of the types described in UnitedStates Letters Patents Numbers 2,220,- 099 and 2,477,383; sodium alkylglyceryl ether sulfonates, especially those ethers of the higheralcohols derived from tallow and coconut oil; sodium coconut oil fattyacid monoglyceride sulfates and sulfonates; sodium or potassium salts ofsulfuric acid esters of the reaction product of one mole of a higherfatty alcohol (e.g., tallow or coconut oil alcohols) and about 1 to 6moles of ethylene oxide; sodium or potassium salts of alkyl phenolethylene oxide ether sulfate with about 1 to about 10 units of ethyleneoxide per molecule and in which the alkyl radicals contain about 8 toabout 12 carbon atoms; the reaction product of fatty acids esterifiedwith isethionic acid and neutralized with sodium hydroxide where, forexample, the fatty acids are derived from coconut oil; sodium orpotassium salts of fatty acid amide of a methyl tauride in which thefatty acids, for example, are derived from coconut oil; and others knownin the art, a number being specifically set forth in United StatesLetters Patent Nos. 2,486,921, 2,486,922 and 2,396,278.

(b) Nonionic synthetic detergents may be broadly defined as compoundsproduced by the condensation of alkylene oxide groups (hydrophilic innature) with an organic hydrophobic compound, which may be aliphatic oralkyl aromatic in nature. The length of the hydrophilic orpolyoxyalkylene 'r-adical which is condensed with any particularhydrophobic group can be readily adjusted to yield a water-solublecompound having the desired degree of balance between hydrophilic andhydrophobic elements.

For example, a well known class of nonionic synthetic detergents is madeavailable on the market under the trade name of Pluronic. Thesecompounds are formed by condensing ethylene oxide with an hydrophobicbase formed by the condensation of propylene oxide with propyleneglycol. The hydrophobic portion of the molecule which, of course,exhibits water insolubility,has a molecular weight of from about 1500 to1800. The addition of polyoxyethylene radicals to this hydrophobicportion tends to increase the Water solubility of the molecule as awhole and the liquid character of the product is retained up to thepoint where polyoxyethylene content is about 50% of the total weight ofthe condensation product.

Other suitable nonionic synthetic detergents include:

(1) The polyethylene oxide condensates of alkyl phenol-s, e.g., thecondensation products of alkyl phenols having an alkyl group containingfrom about 6 to 12 carbon atoms in either a straight chain or branchedchain configuration, with ethylene oxide, the said ethylene oxide beingpresent in amounts equal to 5 to 25 moles of ethylene oxide per mole ofalkyl phenol. The alkyl substituent in such compounds may be derivedfrom polymerized propylene, diisobutylene, octene, or nonene, forexample.

(2) Those derived from the condensation of ethylene oxide with theproduct resulting from the reaction of propylene oxide and ethylenediamine. For example, compounds containing from about 40% to about 80%polyoxyethylene by weight and having a molecular weight of from about5,000 to about 11,000 resulting from the reaction of ethylene oxidegroups with a hydro-phobic base constituted of the reaction product ofethylene diamine and excess propylene oxide, said base having amolecular weight of the order of 2,500 to 3,000, are satisfactory.

(3) The condensation product of aliphatic alcohols having from 8 to 22carbon atoms, in either straight chain or branched chain configuration,with ethylene oxide, e.g., a coconut alcohol-ethylene oxide condensatehaving from 5 to 30 moles of ethylene oxide per mole of coconut alcohol,the coconut alcohol fraction having from to 14 carbon atoms.

(4) Long chain tertiary amine oxides corresponding to the followinggeneral formula, R R R N- 0, wherein R is an alkyl radical of from about8 to about 18 carbon atoms, and R and R are each methyl or ethylradicals. The arrow in the formula is a conventional representation of asemi-polar bond. Examples of amine oxides suitable for use in thisinvention include dimethyldodecyl amine oxide, dimethyloctylamine oxide,dimethyldecyla'mine oxide, dimethyltetradecylamine oxide,dimethylhexadecylamine oxide.

(5 Long chain tertiary phosphine oxides corresponding to the followinggeneral formula RRR"P- O wherein R is an alkyl, alkenyl ormonohydroxyalkyl radical ranging from 10 to 18 carbon atoms in chainlength and R and R" are each alkyl or monohydroxyalkyl groups containingfrom 1 to 3 carbon atoms. The arrow in the formula is a conventionalrepresentation of a semi-polar bond. Examples of suitable phosphineoxides are:

dodecyldimethylphosphine oxide, tetradecyldimethylphosphine oxide,tetradecylmethylethylphosphine oxide, cetyldimethylphosphine oxide,stearyldimethylphosphine oxide, cetylethylpropylphosphine oxide,dodecyldiethylphosphine oxide, tetradecyldiethylphosphine oxide,dodecyldipropylphosphine oxide,

dodecyldi (hydroxymethyl) phosphine oxide, dodecyldi (Z-hydroxyethyl)phosphine oxide, tetradecylmethyl-Z-hydroxypropyl phosphine oxide,oleyldimethylphosphine oxide, and 2-hydroxydodecyldimethylphosphineoxide.

(c) Ampholytic synthetic detergents can be broadly described asderivatives of aliphatic secondary and tertiary amines, in which thealiphatic radical may be straight chain or branched and wherein one ofthe aliphatic substituents contains from about 8 to 18 carbon atoms andone contains an anionic water solubilizing group, e.g., carboxy, sulfo,sulfato, phosphate, or phosphono. Examples of compounds falling withinthis definition are sodium-3- dodecylaminopropionate andsodium-3-dodecylaminopropane sulfonate.

(d) Zwitterionic synthetic detergents can be broadly described asderivatives of aliphatic quaternary ammonium, phosphonium, and sulfoniumcompounds, in which the aliphatic radical may be straight chain orbranched, and wherein one of the aliphatic substituents contains fromabout 8 to 18 carbon atoms and one contains an anionic watersolubilizing group, e.g., carboxyl, sulfo, sulfato,

' phosphato, or phosphono. Examples of compounds fallinghexadecylammonio) -2-hydroxy propane-1-sulfonate which are especiallypreferred for their excellent cool water detergency characteristics.

The non-soap anionic, nonionic, ampholytic and Zwitterionic detergentsurfactants mentioned above can be used singly or in combination in thepractice of the present invention. The above examples are merelyspecific illustration-s of the numerous detergents which can findapplication within the scope of this invention.

The foregoing synthetic non-soap detergent compounds can be made intoany of the several commercially desirable composition forms, forexample, granular, flake, liquid and tablet forms.

Also, it will be understood that the compositions may contain adjuvants,diluents and additives, inclusive of germicidal agents, suds boosters,suds depressants, antitarnishing agents, and anti-bacterial agents, andthe like without detracting from the advantageous characteristics of themixtures.

In general, in the compositions of this invention, the essentialingredients are (a) a detergent substance as set forth above and (b) abuilder mixture, as hereinafter described more at length.

The specific action of the builder mixtures of this invention will varyto some extent depending upon the ratio of active detergent to buildermixture in any given detergent composition. There will be considerablevariation in the strengths of the washing solutions employed bydifierent housewives, i.e., some housewives may tend to use less or moreof the detergent compositions than will others. Moreover, there will bevariations in temperature and in soil loads as between washingoperations. Further, the degree of hardness of the water used to make upthe washing solutions will also bring about apparent diflerences in thecleaning power and whiteness maintenance results. Finally, diiferentfabrics will respond in somewhat different ways to diiferent detergentcom- 7 positions. The best type of detergent composition for houesholduse would in theory be a composition which accomplishes an excellentcleaning and whiteness maintenance effect under the most diversecleaning conditions. The built detergent compositions of this inventionare especially valuable in this respect.

The builder mixtures taught herein are very efficient, and, in general,can be used to permit the attainment of equal detergency with a smallertotal quantity of builder in relation to the total quantity of activedetergent ingredient. It may be stated that useful degrees of build ingactivity may be attained in the practice of this invention with ratiosof active ingredient to builder mixture of from about 1:0.5 to about1:10.

In vew of the wide permissible variations in the ratio of activedetergent substance to builder, the best way to demonstrate thesynergistic action on which this application is based is to select agood detergent composition containing a widely used inorganicbuilder-STP- and substitute difierent quantities of EHDP or EHDP and NTAfor corresponding quantities of STP on a molar basis. This was done inExample I which follows:

EXAMPLE I A solid, heavy-duty detergent composition was made upaccording to the following formulation, wherein the percentages aregiven by weight:

Percent Sodium tallow alkyl sulfate 20 Builder 50 Sodium silicate 6Sodium sulfate Remainder A series of additional compositions were madeup, differing from the above in that various quantities of EHDP or EHDPand NTA were substituted for like quantities of sodium tn'polyphosphateand for each other, on a molar basis. Thus, compositions were made up inwhich the builder consisted entirely of poly-phosphate, in which thebuilder consisted entirely of NTA and in which the builder consistedentirely of EHDP, together with intermediate compositions in which thebuilder mixture contained varying amounts of both EHDP and NTAsubstituted in molar proportions for molar equivalents of thepolyphosphate, as well be evident from the drawing. In some buildermixtures EHDP and NTA completely replaced the polyphosphate. In all themixtures of builders, at least molar percent of EHDP was present.

These several compositions were tested as follows:

Naturally soiled garments and also whiteness cloths were Washed with theabove detergent formulations for ten minutes in an agitator-type washingmachine. The water solution had a pH of about and was at 130 F., thewater hardness was 7 gr./gal. and the product concentration in the waterwas 0.10%. After washing, the garments and whiteness cloths werevisually compared with similar pieces, sirnilarly soiled, and washed inlike detergent formulations differing only in the composition of thebuilder.

It will be understood that because of the dilference in molecular weightof EHDP, NTA and STP there occurred a progressive small variation in theweight percentage as more and more EHDP or EHDP and NTA was substitutedfor STP in a molar basis; but all other conditions remained the same.Thus the tests gave a direct comparison between EHDP, NTA, STP andvarious mixtures of these substances (i.e., EHDP+STP; EHDP-i-NTA; andEHDP+STP+NTA) on a mole-formole basis.

The visual comparison of the washed materials was made by a group offive people for each test who were unfamiliar with the purpose of thetest and who formed their judgments independently. Separate comparisonswere made for cleaning and for whiteness maintenance. The combined datafrom the visual judgments were recorded on a scale such that zerorepresented the cleaning ability or whiteness maintenance of thecomposition containing STP as the sole builder, and higher valuesrepresented the cleaning ability or whiteness maintenance of superiordetergent formulations using mixtures of EHDP-i-STP, EHDP-l-NTA orEHDP+NTA+STP. Significant and consistent higher score values demonstrateclearly superiority in the respective areas of cleaning ability and/orwhiteness maintenance, each area being a measure of detergency building.

The results of the tests outlined and other tests permitted the drawingof certain conclusions which were used to establish the proportions ofbuilder components of the builder mixtures of this invention as setforth in the triangular diagram of the drawing. The triangular diagramis of the conventional type with each corner representing 100% of thebuilder component indicated thereon. The lines on the diagram eachrepresent 10 molar percent. The boundaries of the areas of superiorbuilder performance are defined by the following points:

A85% STP; EHDP B-10% NTA; 85% STP; 5% EHDP C84% NTA; 5% EHDP; 11% STP D%EHDP; 80% NTA E80% EHDP; 20% NTA F10% STP; 90% EHDP G-75% STP; 10% NTA;15% EHDP H-l5% NTA; 75% STP; 10% EHDP I5% EHDP; 44% NTA; 51% STP J10%EHDP; 80% NTA; 10% STP K30% EHDP; 70% NTA L% EHDP; 30% NTA M% EHDP; 10%STP; 10% NTA N30% EHDP; 50% STP; 20% NTA O-20% EHDP; 50% STP; 30% NTAP-20% EHDP; 40% STP; 40% NTA Q30% EHDP; 20% STP; 50% NTA R40% EHDP; 10%STP; 50% NTA S50% EHDP- 10% STP; 40% NTA T50% EHDP; 20% STP; 30% NTAU40% EHDP; 40% STP; 20% NTA Conclusions were as follows:

(1) Any of the three combinations of builder substances (EHDP-l-NTA,EHDP+STP, EHDP+NTA+STP) within the area ABCDEF on the triangular diagramof the drawing gave results superior to EHDP, STP or NTA used alone.

(2) It was found that the superior building results obtained with suchcombination requires the presence of at least 5 molar percent of EHDPshowing that EHDP is a key component in these builder combinations.

(3) As to the binary combinations of EHDP and STP, superior buildingresults were found in the molar ranges of 90% to 15% EHDP and 10% toSTP. Especially preferred molar ranges are 85% to 40% EHDP and 15 to 60%STP. The optimum combination is 60% EHDP and 40% STP on a molar basis.

(4) As to the binary combinations of EHDP and NTA, superior buildingresults were found in the molar ranges of 80% to 20% EHDP and 20% to 80%NTA. Especially preferred molar ranges are 70% to 30% EHDP and 30% to70% NTA. The optimum combination is 50% EHDP and 50% NTA on a molarbasis.

(5) An especially preferred range which gives building results not onlysuperior to those afforded by any of the individual components when usedalone, but also building results at least equal to any mixtures of STPand EHDP, includes ternary builder mixtures containing EHDP, NTA and STPand binary builder mixtures of EHDP and NTA in the molar proportionswithin area GHUKLM on the triangular diagram of the drawing. Thissuperiority was particularly demonstrated where the washing was carriedon in water having a hardness of 7 grains per gallon and in the area ofwhiteness maintenance.

(6) Optimum results were obtained in 7 grain water with a buildermixture consisting of STP, NTA and EHDP within area NOPQRSTU on thetriangular diagram of the drawing.

It is an advantage of many of the various building mixtures hereindisclosed that they may contain substantial quantities of STP which atpresent is considerably less expensive than the other components.

An increase in the hardness of the water used to make up the washingsolution affects the activity of the various builder mixtures describedherein. But optimum results can still be attained with harder waters bya shift in the percentages of ingredients, and more particularly by anincrease in the relative amount of EHDP as respects the other componentsor component. For example, where the water used to make up'the washingsolution has a hardness of 21 grains per gallon, optimum results can beachieved through the use of a ternary builder mixture containing from 40to 60% EHDP, the balance of the mixture being made up of STP- and NTApreferably in about equi-molar proportions. By the same token, improvedresults in waters harder than 7 grain can be achieved Within the rangesset forth above by working toward the upper values of EHDP content or bysomewhat increasing the EHDP content at the expense of NTA and STP, oreither of them.

It will be understood that the ratio of builder to active ingredient oringredients can be varied within the range given above for the obtainingof particular results.

It will be understood by the skilled worker in the art that detergentcompositions, including the compositions of this invention, willordinarily contain various ingredients for special purposes. Thus, theycan contain suds builders, suds depressants, anti-corrosion agents,antiredeposition agents, dyes, fluorescers, perfumes and the like,without interfering with the basic characteristic of this invention. Inthe manufacture of liquid detergents, water or alcohol vehicles ormixtures of the two, together with solubilizing agents and the like, asknown in the art, can be used. These form no limitation on theinvention, but are intended to be includable within the terms of claimscalling for compositions consisting essentially of active ingredientsand builder mixtures in accordance with the teachings herein.

The detergent compositions of this invention are preferably used toprovide a pH in aqueous washing solution within a pH range of about 9 toabout 12; the optimum building effects are obtained within this range.Washing temperatures usually range from about 80 F. to about 200 F.Fabrics are preferably rinsed and dried after washing.

Other exemplary compositions are as follows:

EXAMPLE II Percent Sodium dodecylbenzene sulfonate, derived from apolypropylene which is predominantly tetra- This composition givesexceptional results, in both cleaning and whiteness maintenance,especially in water of 7 grain hardness. It provides a pH in washingsolution of about 10.

EXAMPLE 111 Percent Sodium dodecylbenzene sulfonate, derived from apolypropylene which is predominantly tetrapropylene 17.3 Builder mixtureconsisting of equal parts of sodium tripolyphosphate and EHDP on a molarbasis 43.5 Sodium silicate 5.9 Sodium sulfate 19.6 Monoethanolamide ofcoconut oil fatty acids 2.1 Perfume 1.6 Moisture 10.0

Such a composition provides a pH in water solution of about and givessuperior heavy duty performance as compared with compositions in whichthe sole builder was either EHDP or STP. Even further improvement inperformance, particularly in cool water, can be obtained by replacingthe sodium dodecyl benzene sulfonate with an equal amount of3-(N,N-dimethyl-N-hexadecylammonio)-propane l-sulfonate or 3-(N,Ndimethyl-N- hexadecylammonio) -2-hydroxypropane-l-sulfonate.

Similar good results can be obtained by using as the builder mixture ofthe composition of Example III, 35.3% of a builder mixture consisting ofEHDP and 80% NTA on a molar basis and raising the level of sodiumsulfate to 29.6%, and replacing the sodium dodecyl benzene sulfonatewith an equal amount of the condensation product of a mole of tallowfatty alcohol and 10 moles of ethylene oxide or sodium 3-dodecylamino-propane sulfonate.

10 EXAMPLEIV Percent Sodium dodecylbenzene sulfonate (as in Example '11)Sodium toluene sulfonate 2.0

Builder mixture consisting of sodium tripolyphosphate and 20% EHDP on amolar basis 47.4 Sodium sulfate 14.9 Trichlorocarbanilide 0.5 Sodiumsilicate 6.0 Monomethanolamide of coconut oil fatty acids 1.6 Perfume1.6 Moisture 6.0

When evaluated in a comparative evaluation test, such a formulationexhibits superior cleaning ability and improved whiteness maintenancewhen compared to similar formulae in which sodium tripolyphosphate isthe sole builder. It provides a pH in washing solution of about 10.

Even superior results are obtained in the composition of Example IV byusing as the builder mixture 47.4% of a mixture of 40% EHDP+30% NTA+30%STP or 30% EHDP+40% NTA+30% STP on a molar basis. The sodium salt oflinear dodecylbenzene sulfonate can also be used to advantage.

In the above example builder mixtures were used Which consisted,resepectively, of 40%, 50% and 60% EHDP, with the remainder in each caseconsisting of about equal percentages of STP and NTA on a molar basis.Such compositions provide a pH in washing solution of about 10 and workexceptionally well as regards cleaning and whiteness maintenance inrelatively hard water, i.e., water having a hardness of 21 grains orgreater, While also giving a good account of themselves in softerwaters. Product usage will, of course, be increased as water hardnessincreases.

As an example of a liquid composition having good cleaning and whitenessmaintenance properties which can be made in accordance with theinvention and provides a pH of about 10, the following is given:

EXAMPLEVI Percent Sodium dodecylbenzene sulfonate (as in Example II) 9.0Potassium alkylglyceryl ether sulfonate, the alkyl being derived from amixture of lauryl and myristyl alcohol 4.0 Potassium pyrophosphate 11.NTA (as potassium salt) 3.75 EHDP (as potassium salt) 3.15Monoethanolamide of coconut oil fatty acids 3.0 Potassium toluenesulfonate 8.5 Ethanol 4.0 Sodium silicate 4.5 Water, fiuorescers, etc.Balance A similar good heavy duty liquid composition can be obtained bysubstituting for the 18% total builder in the above formula 18% of thefollowing builder mixtures:

A. Equal parts (on a molar basis) of potassium pyrophosphate and EHDP;

B. 40% NTA and 60% EHDP on a molar basis.

1 1 l 2 In the following examples the A columns represent dutylaundering system. Moreover, a builder mixture of conventional builtcompositions; the B columns represent equal molar portions of EHDP and=NTA can advantagecompositions in which the builders of the Acomposiously be employed in a washing solution containing sotions arereplaced on an equal molar basis with builder dium tallow alkyl sulfateand STP in 1:3 ratio by weight,

mixtures of this invention and which provide a pH of 10: 5 e mi e ofEHIDP and NBA being added in an amount by Weight equal to that of theSTP in solution.

VII VH1 IX Modifications may be made in the invention without departingfrom the spirit of it. The invention having been A B A B A B describedin certain exemplary embodiments, what is Sodium tetrapropylene claimedas new and desired to be secured by Letters benzene sulionate 35 35 1717 10 10 Pate t Sodium tallow alcohol n 1 sulfate 0 0 1. A buildermixture composition conslsting essentially 2'15 g g 50 20 50 so of oumpyrop osp a e NTA 11.98 13.95 8.73 (a) the trisodium salt ofethane-l-hydroxy-l,l-drphos- EHDP 3.18 7.4 5. 55 honic acid and Sodiumsilicate 6 6 6 6 6 6 p Monoethauolamide of (b) a builder selected fromthe group consiting of sotiiini uiiitfffiiii::fsaf'iai." B31. B a."sari-in. sodium tripolyphosphate and sodium py p p the trisodium saltof nitrolotriacetic acid, and mix- The builder mixtures of the Bcompositions had the thereof following molar proportions: in which themolar proportions of the components of said VIIB50% STP+sodiumpyrophosphate, 40% NTA, builder mixture are within the area ABCDEF onthe tri- 10% EHDP; 1 angular diagram of the drawing, said compositionprovid- VIIIB40% STP, 40% NTA, 20% EHDP; ing in water solution a pH inthe range of about 9 to IX-B60% STP, NTA, 15% EHDP. about 12.

In the laundering of naturaly soiled fabrics, continued 25 2. A builtdetergent composition consisting essentially use of compositions VII-B,VIII-B and IX-B will .proof sodium tallow alkyl sulfate and the buildermixture vide cleaning and whiteness maintenance superior to cornof claim1 in which the ratio of alkyl sulfate to builder positions VII-A, VIII-Aand IX-A, even though the B mixture is substantially 1:05 to 1:10 byweight. compositions contain, respectively, about 3%, about 9% 3. Thecomposition claimed in claim 1 wherein the and about 6% less builder byweight. builder mixture contains subtantially equal proportionsAdditional examples of detergent compositions emof said tripolyphosphatesalt and said salt of nitrilotriacetic ploying the builder mixtures ofthis invention are shown acid making up about 60 to 40 percent of themixture, in the table below, wherein the .pH of the compositions Withingredient (a) making up about 40 to 60 percent in water solution isabout 10, and the numbers are perthereof, all on a molar basis. centagesby weight. These examples demonstrate some 4. A builder mixturecomposition consisting essentially of the builder-active detergentcombinations which can f be made. These are then preferably formulatedwith the (a) the trisodium salt of ethane-l-hydroxy-l,l-diphosvariousother materials normally found in complete dephonic acid,

tergent products such as antiredeposition agents, sodium dium triplyphosphate, and silicate, perfume, suds depressants and the like. Thetotal the trisodium salt of nit-rolotriacetic acid actlve P builder canVary wldely- In normal general and in which the molar proportions of thecomponents of P p detergents this total amounts to 5090% of the saidbuilder mixture are within the area GHIJKLM on complete product. In thsoall d l g t y Products the triangular diagram of the drawing, saidcomposition and in liquids, the sum is often considerably less, theproviding in water solution a pH in the range of about balance usuallybeing a diluent such as water. 9 to about 12.

X XI XII XIII XIV XV XVI XVII XVIII XIX XX Builder mixture of 40% EHDPplus 30% NTA plus 30% STP on a mo ar Dodecylmethyl sulfoxide 15Dodecyldimethyl phosphiue oxide 25 -20 condlensation product of one moleof dodeeauol and 6 moles of ethylene 2 oxi e t 15 5 Condensation productof one mole of tridecyl phenol and 10 moles of ethylene oxide 203-(N,N-dimethyl-N hexadecyl ammonio) propane-1-sulfonate .t 353-(N,N-dimethyl-N dodecylammonio) 2-hydroxy propane l-sulfonate 15 15Disodium dodecyl fl-irm'no dipropionate Sodium 3-dodecylamiuoprop anesull'onate. (N,Ndimethyl-N dodecyl ammonio) acetat Reaction product ofdodecylamiue with sod th uate (U 1 Patent 2,658,072) 10 Excellentdetergent compositions can also be prepared 5. The composition claimedin claim 4 wherein the by using in each of the above Examples X-XX abuilder molar proportions of the components of said builder mixmixtureof EHDP+'-5()% NTAtmolar percentages) ture are within the area NOPQRSTUon the triangular or a builder mixture of 50% EHDP+50% STP (molardiagram of the drawing.

percentages) instead of the recited ternary builder mix- 6. A builtdetergent composition consisting essentiall ture. of sodium tallow alkylsulfate and the builder mixture Any of the builder mixtures diclosedherein, especially of claim 4 in which the ratio of alkyl sulfate tobuilder those in each of the examples, can be used beneficially mixtureis substantially -1:0.5 to 1:10 by weight. as an additive to washingsolutions containing an organic 7. A built detergent compositionconsisting essentially synthetic detergent with little or none ofconventional of sodium tallow alkyl sulfate and the builder mixturebuilders. For example, a builder mixture of 40% of claim 5 in which theratio of alkyl sulfate to builder EHDP+30% NTA +30% STP (molarpercentages), mixture is substantially 1:0.5 to [1:110 by weight.

can be added to a washing solution of sodium linear do- 8. A buildermixture composition consisting essentially decyl benzene sulfonate toprovide an outstanding heavy 7 5 of 13 (a) the trisodium salt ofethane-1-hydroxy1,1-diphosphonic acid, and (b) sodium tripolyphosphate,

in which the molar proportions of the components of said builder mixtureare 90% to 15% component (a) and to 85% component (b), said compositionproviding in water solution a pH in the range of about 9 to about 12.

9. The composition claimed in claim 8 wherein the said molar proportionsare 85% to 40% component (a) and to 60% component (b).

10. A builder mixture composition consisting essentially of (a) thetrisodium salt of ethane-l-hydroxyl,l-diphosphonic acid, and

(b) the trisodium salt of nitrilotriacetic acid in which the molarproportions of the components of said builder mixture are 80% tocomponent (a) and t 20% to 80% component (b), said composition providingin Water solution a pH in the range of about 9 to about 11. Thecomposition claimed in claim 10 wherein the said molar proportions are70% to component (a) and 30% to component (b).

References Cited UNITED STATES PATENTS 3,151,084 9/1964 Schiltz et a1.252-137 3,159,5 8'1 "12/1964 Diehl 252-152 3,122,417 2/1964 Blaser eta1. 26046 1.310

FOREIGN PATENTS 1,072,346 '12/ 1964 Germany.

889,670 2/ 1962 Great Britain. 1,082,235 5/ 1960 Germany.

927,617 5/1963 Great Britain. 1,107,207 5/ 1961 Germany.

925,373 5/1963 Great Britain.

LEON D. 'ROSDOL, Primary Examiner.

20 ALBERT T. MYERS, JULIUS GREENWALD, MAYER WEINBLATT, Examiners.

